Sulphopolycarboxylic acid amides



Patented Apr. 29,1341 v uNi'rEo sra 1;. s. PATENT azaavzo f smnoromcannoxmo ACID amass Morris Katzman, Chicago, 111., assignor to The Emuls'ol Corporation, Chicago,1ll a corporation oi! Illinois a N6 Drawing. Application July '27, 1939, Serial No. 288,777

-15 Claims. (or 260-401) This invention relates to new. chemical com- 'l'he acyi radical p unds in the form of sulphonic derivatives which y are characterized by possessing interface modiiy- .1

' o I! ing properties rendering the same highly useful R43 for th purposes for whichlsuch agents are 5 in the above formulae may be of aliphatic, cycloployed in the various arts, aliphatic, aromatic or aromatic-aliphatic char- At leasgmost of the novel sulphonic compound; acter, as will be pointed out hereinafter, and may fall within the scope ofthe general formulae contain subsfltuent g'mups Such ammo halo gen, hydroxy, sulphate, 1119 111 D fl '0 carboxyl, Iiitrile, and the like, but it is particular- Rf|!NY-(alkNX"),.-O c co-r .ly preferred that it he unsubstituted aliphatic or fatty and contain from twelve carbon atoms to (s 01M)... eighteen carbon atoms. Z and alk may also each RC--NY-r-(CXFCXg-NX),.-OC-z.--CO-T' contain substituent groups such as those men- II v l5 tion'ed and thesequence of carbon atoms there- 5 in may be interrupted by O, S, C=O, NH, NR l' where Bis alkyl, and the like.

a o The substances of the invention may also be i; considered as derivatives of polyamines in which a a 20 hydrogen oil at least two different amine groups is an yl ra ical cont inin at le four is replaced-by different radicals, (1) a carboxylic hon atoms-and particlflarly from twelve to eightacyl radical containing at least four but prefereen carbon atoms, Y. X, dx" are the Same ably from eight "to; eighteen carbon atoms, and dissimilar members Selected f the group --(2) a carboxylic-acid acyl radical of a sulphoconsisting of hydrcgen.alky1o1 y ,and cyc a -eri polycarhoxylic', acid, particularly aliphatic sulkyl, all: is a hydrocarbon residue, saturated or phodicarboxyflc and having t more t a eight unsaturated, with or without interruptions or carbon t ms, 1 1, is a residue. generally a n- In order. that the nature of the invention may hydrogen aacid c011- .becomeapparent, there are listed hereinbelow taining. preferably less than eight carbon atoms, 30 representative compounds which fall within the T is (l) a; member of the group comprising-NHR scope f t v where R is hydrogen, lower alkyl, hydroxy-alkyh and cycloalkyl, and (2) OY. where Y is a cation, (1)

. n lower alkyl, cycloalkyl and aliphatic polyhydric =.N alcohol radicals, M is a cation, m is a whole num- 33 S Oak ber. preferably one or two, and n is a whole num- 2 4 I her.- preferably from one to four.- ll

A more limited aspect of the compounds of the? l' Q C'OHrCECOONE invention, may be represented by the general aNa formula a 4o. 3 f f,

H I ohmsd-Nn-cn-om-hmoc-cm-cm-orao00x 0 v IOM I I i HI 03K wherein a 7 I II a v is an acyl radical containing atjleast eig t and preferably from twelve to eighteen carbon atoms, and M and M are cations.-

OaH

-mr-cni-o rh-Nn-o C-CHrCH-COONHi O aH-NE(C:HO H): (a Bic-03: o

- (m i I 6 While the above examples represent single submflrcflncflrmwcrfm I stances, it will be understood that in practice it CuHu-C-NHCHg-CHzNHOCCH-B clue, is, in general, moreadvantageous to employ mixture of any two or more thereof with or without -diluents.

(l QnHa-C-NH-CHOHs-NH-OG-QHa-CHrCH-COOH 2, In a the compounds are prepared. by

. s 01H initially reacting a polyamlne. for example, ethyli (13) o i 1 one diamine (HaN--C2H4NH:). .with a higher I! v molecular weight carboxylic acid or derivative GH'PCNH(C'H NH)POCCHPCH C 3 thereof,- such as an ester or halide, undericondi- (M) b tions. such as to insure a substantial yield of g amide. The resulting amide is then reacted with v on mn-cim-rlmoG-(CHrJa-fiiH-CIh-GEW K a lower molecular weight aliphatic unsaturated poly-carboxylic acid or anhydride or a halogenan a a f H (1 0|1Hn-CNH-GaH|NB-0C--CHt-CH-OHL1OONE-CHr-Hw-CHNH 05K n p poly=cerhoxylic acidor halide or otherderivative 1 thereoi to produce the unsaturated ester or halo- C Y gem-continuing ester, and then with a salt of sul- (m 80am phurous acid as an alkali sulphite or bisulphite to introduce a sulphonic group into the u c molecule. It will be clear, of course, that the c NH RENE 0C GHPCH .COOK order oi the steps may be reversed ii desired; (18) 01K that is, the-reaction with the higher molecularweight acid or derivative thereof maybe carried v a out last, or the two amidiflcation steps may be cam-c NH C'HPS-(FHrNH 0c cnr'cuwoox carried out in optional order and the reaction (19). OIK with'the alkali sulphite or the like may be car'- E rled out thereafter. 1 Still another method comprises initially. precm NH 0 NH oc-cn 011-000:

T paring the aliphatic sulpho-poly-carboiwlic acids, (-20) or'their anhydrides'. for example, by reaction of E 4 antunsaturated aliphatic dicarboxylic acid or a cal thereof with an'alkali or like 'blsulphite or Har- NHCCH-GH 0-00 11 NH carby sulphonation of a saturated or unsaturated (21) dicarboxylic acid, and reacting the resulting sulg N n pho-polycarboxylic acid with a carboxylic acid amide such as the lauric acid amide oi ethylene c'flrc NH (bur-N c H Hr c0 diamine. "Alternatively, the aliphatic sulphoam mly-carboxylic acid or its anhydrlde may be re- (22 .0 some 0H. acted with a free amine, for example, diethylene an acyl halide, or other derivative, such as octoyl 03) p i I e 35 chloriclelauroyl bromide, or the like The following examples are illustrative of Q fmethods which have been found suitable for pre-'- flinhzwifl h paring various oi the compounds which are dis- (A) i closed herein. It will be appreciated that other Cima-CN -C:1t-NHfiCHrCH-COOH.H:N- 7o methods may be utilized, that the proportions of o gl gm l triamine, and the resulting product reacted with o reacting ingredients, times of reaction, order of M I G steps, and temperature may be varied and that supplementary processes of purification and the OhHzr-{i-diH-CzBle-N--C:Hr-NH-CCH:-C "CO0K like may be resorted to wherever round desirable 5 '75 or convenient. These and other variations and 'portion of a compound modifications will be evident tothoseskilled in the art in the light of the guiding principles which are disclosed herein,

' Example A (1) 107.2 grams of the methyl ester of a mixture, 01' substantially equal parts of lauric and myristic acids and 52.6 grams oi hydroxy ethyl ethylene diamine were heated together for a period of 1 /2 hours, with stirring, at a temperature from 160 degrees C. to 250 degrees C.

(2) 31 grams of the product produced in part .(1) hereof and 11 grams-of maleic anhydride were warmed to 50 degrees C., with stirring, whereupon the temperature spontaneously rose to 90 degrees C. where it was maintained for a few minutes.

(3) 12.3 grams of the reaction product produced in part (2) hereof, 6.6 grams or sodium bisulphite and 40 cc. of water were heated for 10 minutes, with stirring, at 60 degrees C. to ill degrees C.

The final product was a clear liquid, possessed good foaming properties in both acid and alkali aqueous media. and contained a substantial prohaving the following a-c is the acyl radical corresponding to the mixture of lauric and myristic acids).

Example B 10 grams of the reaction product produced in part (1) of Example A hereinabove and 7 grams of sulpho maleic anhydride were mixed together CaHaOH R-fi,-NH-C,HlN-( :-c=cH-o00K is the acyl radical corresponding to the mixture of lauric and myristic acids).

Example C (1) To 30.4 grams of a 70% aqueous solution of ethylene diamine 25 cc. of water were added and then 39.2 grams of maleic anhydride were added slowly and with stirring. The temperature spontaneously rose from 25 degrees C. to F degrees C. The reaction mass was then cooled to 20- degrees C. and there were added thereto, slowly and while stirring and cooling, 16. 3. grains of sodium hydroxide previously dissolved in "15 cc. of water. The temperature rose to apprommately 30 degrees C.

(2) To the reaction product oi part (1) hereof there were added dropwise, with stirring and cooling, 87.2 grams of lauroyl chloride and simul-- taneously therewith there were also added, dropwise and with stirring, 16.4 grams of sodium hydroxide previously dissolved in 100 cc. of water. The addition of the lauroyl chloride and the solution of sodium hydroxide took place over a period of V hour and the temperature rose to degrees C. The final product was just alkaline to phenolphthalein. v p

(3) To the reaction product of perv-(2) hereof, there were added cc. of water, and 83 grams of sodium bisulphite previously dissolved in 50 cc. of water. The resulting mass was stirred at 60 degrees C. for approximately 15 minutes.

(4) One-half of the reaction mass of part 3) hereof was allowed to dry in the atmosphere and ,the drying was then finished in an oven at degrees C., the residue being a powder having good foaming properties. I I

(5) grams of the reaction product of part (3) hereof were mixed with 1000 cc. of boiling isopropyl alcohol and the mass was filtered. The

precipitate, which contained the desired compound together with inorganic ingredients, was soluble in water and had good foaming properties.

The product of parts (4) and (5) hereof contained a substantial proportion of a compound having the following probable formula:

.of Example A hereinabove were dissolved in 25 cc. of dioxa'ne and there were added thereto, slowly and with stirring, 10 grams of molten sulpho phthalic anhydride. The temperature rose from. 40 degrees C. to 95 degrees C. After a few minutes, 200 cc.of isopropyl alcohol were added to the reaction mixture and the mass was cooled to Bil-35 degrees C. and then neutralized with 150 cc. of approximately 0.5 N alcoholic potassium hydroxide, the reaction mass being just neutral to phenolphthalein. The precipitate was allowed to settle and the alcoholic solution was then decanted therefrom. In order to dry the precipitate, 100 cc. of ethyl ether were added thereto and" mixed well and then filtered on the Buchner funnel. The final reaction product was a cream colored powder, quite hygroscopic, very soluble in; water, had good'foaming and detergent properties and contained a substantial proportion of a compound having the following probable formula;

The acyl radical represented by M0 in the general formulae may, as stated, be derived from various sources. Among such sources may" be mentioned straight chain and branched chain carbo'xylic, aliphatic, and fatty acids or derivatives thereof such as halides, saturated and unsaturated, such as butyric acid, caprylic acid, caproic acid, capric acid, sebacic acid, hehenic acid, arachidic acid, carotid acid, erucic acid, melissic acid, stearic'acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above-mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard,

coconut oil, rapeseed oil, sesame oil, palm kernel nauba wax and carboxylic acids derived, byv

oxidation and other methods, from petroleum; cycloaliphatic and hydro-aromatic acids such as hexahydrobenzoic acid, resinic acid, naphthenic acid and abietic acid; aromatic acids such as phthalic acid, benzoic acid, naphthoic acid, pyridine carboxvlic acids;hydroxy aromatic acids such as salicylic acid, hydroxy benzoic and naphthoic acids, and the like; and Substitution and addition derivatives, particularly halogen substitution and addition derivatives of the aforementioned carboxylic substances. It will be understood that mixtures of any two or more of said acids may be employed if desired.

The sulpho-poly-carboxylic acid radical of the compounds of my invention may be selected, among others, from the following illustrative members: sulphofumaric acid, sulphomaleic acid,

sulphosuccinlc acids, sulphomalonic acid, sulphoglutaric acid. sulphoadipic acid, sulphopimelic I acid, sulphoazelaic acid, sulphocit'raconic acid, sulphosebacic acid, sulphomesaconic acid, sulphosuberic acid, sulphoaconitic acid, sulphoitaconic acid, sulphoglutaconic acid, sulphomucic acid, aromatic ssulpho-polycarboxyllc acids such as sulpho-phthalic acids, and the like. The sulphopoly-carboxylic acid radicals may, in certain reactions may be selected from a large group,

particularly in the alkylene polyamines and poly- I alkylene polyamines and the alkyl and aralkyl derivatives as, for example, ethylene diamine, piperazine, diethylene triamine, triethylene tetraamine, mono-methyl ethylene-diamine, benzidine,

' phenylene diamines such as orthophenylene diamine and paraphenylene diamine, mono-ethyl diethylene triamine, beta-dimethyl-amino-ethyl amine, and the like.

In the event that the sulphonic compounds of the present invention are made by reacting the halogen derivatives with an alkali sulphite or other soluble sulphites as well as thiosulphates, the corresponding alkali sulphonic acid derivative is produced. When prepared by other methods,

other sulphonic acid salts may be produced, or the alkali sulphonates can be converted into other salts by methods such as described in the-application of Benjamin R. Harris, Serial No. 190,136,

filed February 11,-1988. Thus, the cation represented by M in the general formulae set forth hereinabove may be calcium, magnesium, aluminum, zinc, organic nitrogenous bases as, for example, alcohol amines and alkylol-, aryloland aralkylol amines including mono-, diand triethanolamine and mixtures thereof such as are,

the paper pulp or the like.

for example. present in so-called commercial triethanolamine, propanolamines, butanolamines,

,penta'nolamines, 'hexanolamines, glycerolamines,

dibutyl ethanolamine, diethanol ethyl amine, cyclohexyl ethanolamine, diethanol cyclohexylamine, ethanol aniline, alkylol polyamines such as alkylol derivatives of ethylene diamine, monomethyl monoethanolamine, diethyl-monoetha-- nolamine, l-,-amino-2,3-propanediol, v1,2-diaminopropanol; alkylamines such as butyl amine, hexylamine, dimethylamine, ethylene diamine, diethylene triamine, triethylene tetra-amine, mono-methyl ethylene diamine, mono-ethyl diethylene tetra-amine, 'mono-allyl amine, aro-.

'matic and heterocyclic bases such as benzylamine, cyclo hexylethyl aniline, morpholine, pyridine, alkyl pyridines such as methyl-pyridine,

piperidine, 'pyrrolidines, quinoline, quinaldine,

nicotine, and homologues. and derivatives or substitution products thereof; mixtures of any two or more thereof, and the like.

It will be understood that these organic bases, as in the case of triethanolamine, for example, may be employed in pure, impure, or commercial form.

The compounds of this invention have utility in various arts in which interface .modifying agents are employed. They are resistant to precipitation by calcium and magnesium salts and are compatible with acid and alkali media. They maybe utilized in washing and laundering and in the textile and related industries wherein they function for softening, wetting, detergent, emulsifying, penetrating, dispersing, frothing, and foaming purposes. The textiles, various treatments of which in the prese'nceof the agents of the present invention are rendered effective, comprise natural products such-as cotton, wool. linen, and the like, as well as the artificially produced fibres (and fabrics), such as-rayon, cellulose acetates, cellulose ethers and similar artificial products. It will be understood, of course, that the agents may be used in aqueous and other media either alone or in combination with other suitable salts of organic or inorganic character or with other interface modifying agents. In the dyeing of textiles they may be employed as assistants in order to bring about even level shades. They may be used in the leather industry as wetting agents in soaking, dyeing, tanning and the softening and other treating baths for hides and skins. Theirutility 'as emulsifying agents enables them to be employed for the'preparation of emulsions which may be used for insecticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of cosmetic creams such as cold creams, vanishing creams, tissue creams, shaving cream of the brushless and lathering type and similar cosmetic preparations. Another use to which the agents of the present invention may be placed is for the treatment of paper pulp and paper where they may be employed, for example, as penetrating agents in the cooking of Their capillary or interfacial tension reducing properties enables them to be employed in the fruit and vegetable industry in order to eilectthe removal from fruits and .the like of arsenical and similar sprays. They possess marked utility in the ore dressing industry wherein they function effectively in froth flotation and agglomeration processes. Their interface modifying properties also permit their use in lubricating oils and the like enabling the production of effective boring oils, cutting oils, drilling oils, wire drawing oils,

. in rubber compositions, for breaking or demulsi- 1 fying petroleum emulsions such as those of thewater-in-oil type which are encountered in oiliield operations, and for various other purposes V which will readily occur to those versed in the art in the light of the disclosure herein.

As detergents, they may be employed for the preparation of shampoos, dentifrices and the like. In general, they may be dissolved in water or aqueous media and utilized in that form or, in the case of solid products, they may be packaged and sold in such form preferably mixed with diluents. They may also be utilized for commercial cleansing, laundering and washing operations with marked advantage. g

The products of the present invention may be employed alone or together with lesser or greater quantities of inorganic or organic compounds. Thus, for example, they may be employed together with salts such as sodium chloride, alkali metal phosphates including pyrophosphates and tetraphosphates, sodium sulphate, alums, perborates such as sodium perborate and the like. They may be utilized in alkaline or acid media in the presence of sodium carbonate, sodium bicarbonate, dilute acids such as, hydrochloric, sulphurous, acetic and similar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophillic gums including pectinjtragacanth, karaya, locust bean, gelatin, arabic and the like, glue, vegetable, animal, fish and mineral oils, solvents such as carbon tetrachloride, monoethyl ether of ethylene gylcol, monobutyl ether of ethylene glycol, monoethyl and monobutyl ethers of diethylene glycol, cyclohexanol, and the like; They may be used together with wetting, emulsifying,

tetraphosphoric acid esters of. higher molecular weight alcohols; Turkey-red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and other classes of wetting agents.

It will be understood that, in all cases, there is present in the molecules of the sulphonic derivatives of the present invention at. least one sulphonic acid radical, although, depending upon the particular reacting ingredientsv and the proportions thereof utilized, more than one sulphonic group may be introduced.

Wherever the term higher" is employed as referring to higher molecular weight organic Whenever the, term sulpho poly-carboxylic acid radical, sulpho-dicarboxylic acid radical, sulpbo-succinic acid radical, or the like expres- .sion is employed in the claims, it will be understood to cover the compounds irrespective of whether the'hydrogen of the sulphonic or carboxyli'c acid radical is present as such or replaced by another cation, unless the connotation otherwise expressly indicates differently.

wherein The present application is a continuation-inpart of application, Serial No. 222,779, filed August 3, 1938, now Patent No. 2,198,806, issued April'30, i940.

, What we claim as new and desire to protect by Letters Patent of the United States is:

i. A chemical compound corresponding to the general formula is an unsubstituted acyl radical containing at least four carbon atoms, Y and X" are members selected from the group consisting of hydrogen, alkyl, cycloalkyl and alkylol, alk is a member selected from the group consisting of hydrocarbon and substituted hydrocarbon residues, Z is the residue of an aliphatic poly-carboxylic acid, '1 is (1) a member of the group NHR' where R is hydrogen, lower alkyl, hydroxyalkyl, or cycloalkyl, and (2) OY where Y is a cation, lower alkyl, cycloalkyl and aliphatic polyhydric alcohol radicals, M is a cation, and m and n are small whole numbers.

2. Chemical compounds corresponding to the general formula wherein Y, x, X and X" are members selected from the acids or the like; it will be understood to cover at least eight carbon atoms unless otherwise specifically stated and, concomitantly, the term lower will mean less than eight carbon'atoms.

group consisting of hydrogen, alkyl, cycloalkyl and alkylol, Z is the residue of an aliphatic dicarboxylic acid containing not more than eight carbon atoms, T is (1) a member of the group NHIR. where R is hydrogen, lower alkyl, hydroxyalkyl, or cycloalkyl and (2) QY where Y is a cation, lower alkyl, cycloalkyl and aliphatic polyhydric alcohol radicals, M is a cation, m is one or two, and n is a small whole number.

3. Chemical compounds corresponding to the general formula a a i wherein is a fatty acid acyl radical containing from 4; Chemical compounds corresponding to the general formula wherein R-i is an acyl. radical containing from twelve to eighteen carbon atoms, and M and M are cations.

5. Chemical compounds corresponding to the general formula v I SOsM wherein n is a small whole number and M and M are alkali metal cations. 1

6. Chemical compounds corresponding to the general formula wherein His is an aliphatic acyl radical containing at least eight carbon atomax, X and X" are members "elected from the group consisting of hydrogen,

aikyl, cycloalkyl and alkylol, Z is a hydrocarbon residue of an aliphatic dicarboxylic acid containing not more than eight carbon atoms, M is a cation, M is an organic nitrogenous base cation, and n is avwhole number.

7. Chemical compounds corresponding to the general formula .soM

is an aliphatic acyl radical containing from eight to eighteen carbon atoms, alk is an aliphatic hydrocarbon residue, M and M are cations, and I n is a whole number.

'8. Chemical compounds corresponding to the general formula wherein i R-C is a fatty acid acyl radical containing from eight to eighteen carbon atoms, M and M are alkali metal cations, and n is a whole number.

succinic acid.-

consisting of carbonlic acids and derivatives thereof containing at least four carbon atoms to produce a substantial yield of an amide of said poLvamine, then reacting the resulflng amide with a member selected from the group-consisting of aliphatic unsaturated poly-carboxylic acids, anhydrides thereof, and aliphatic halogeno-poly-- carboxylic acids and halides thereof, followed by reactingthe resulting productwitha salt ofsulphurous acid.

11. The method of claim 10 wherein the polyamine falls within the scope of the formula where X and x' are members. selected from the group consisting of hydrogen. alwl, cyclcalkyl and alkylol, and n is an integer at least one.

13. The method of claim 10 wherein the polyamine falls within the scope of the following formula wherein n is an integer. at least one, and the polycarboxylic-acid or derivative thereof is selected from the group offumaric acid, malei acid, and maleic anhydrlde.

13. A poiyamine in which hydrogen of an amine group is replaced by an imsubstituted carboxylic acyl radical containing at least four carbon atoms, and inwhich hydrogen of a diiferent amine group isreplacedbythe carboxylicacylradicalofan aliphatic-siflpho-poly-carboxylic acid containing not more than eight carbon atoms.

14. Apolyaminein whichhydrogenof an amine group is replaced by an unsubmtuted fatty acid 50 acyl radical containing from twelve to eighteen v carbonatoms,andinwhichhydrcgcnoil-different amine radical is replaced by the carboxylic acyl radical of an aliphatie-mlpho-di-carboxylic acid containing not more than eight carbon atoms.

15. An aliphatic diamine in which hydrogen of one amine group is replaced by the carboxylic acyl radical of an aliphatic carboxylic acid containing from twelve to eighteen carbon atoms, and in which hydrogen 01 the other amine group is replaced by the carboxylic acyl radical of sulpho- Monms xs'rzwm. 

